(E)-6-Bromo-3-{2-[2-(2-chloro-benzyl-idene)hydrazin-yl]thia-zol-5-yl}-2H-chromen-2-one dimethyl sulfoxide monosolvate.

In the title compound C(19)H(11)N(3)O(2)SClBr·C(2)H(6)OS, the mol-ecule adopts an E configuration about the central C=N double bond. The chromene ring system and the thia-zole ring are approximately planar, with maximum deviations of 0.027 (2) and 0.003 (1) Å, respectively. The central thia-zole ring makes dihedral angles of 21.82 (9) and 5.88 (7)° with the chloro-substituted phenyl ring and the chromene ring, respectively. In the crystal, mol-ecules are connected via N-H⋯O, N-H⋯S and C-H⋯O hydrogen bonds, forming supra-molecular chains along the c axis. An intra-molecular C-H⋯O hydrogen bond occurs. π-π inter-actions are observed between the thia-zole and phenyl rings [centroid-centroid distance = 3.6293 (10) Å]. A short Br⋯Cl contact of 3.37 (6) Å also occurs.

Related literature

For details and applications of coumarin derivatives, see Liebig et al. (1974 ▶); Pathak et al. (1981 ▶); Hwu et al. (2008 ▶); Lee et al. (2003 ▶); Siddiqui et al. (2009 ▶). For the synthesis of the title compound, see: Tian et al. (1997 ▶); Yaragatti et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H11BrClN3O2S·C2H6OS

M = 538.86

Monoclinic,

a = 6.5806 (4) Å

b = 15.7789 (9) Å

c = 20.9378 (13) Å

β = 90.684 (2)°

V = 2173.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.24 mm−1

T = 100 K

0.49 × 0.09 × 0.06 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.406, T max = 0.870

37791 measured reflections

6392 independent reflections

5013 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.069

S = 1.00

6392 reflections

290 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.86 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011160/sj5124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011160/sj5124Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H11BrClN3O2S·C2H6OS	F(000) = 1088
Mr = 538.86	Dx = 1.646 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9665 reflections
a = 6.5806 (4) Å	θ = 2.8–29.9°
b = 15.7789 (9) Å	µ = 2.24 mm−1
c = 20.9378 (13) Å	T = 100 K
β = 90.684 (2)°	Needle, yellow
V = 2173.9 (2) Å3	0.49 × 0.09 × 0.06 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	6392 independent reflections
Radiation source: fine-focus sealed tube	5013 reflections with I > 2σ(I)
graphite	Rint = 0.059
φ and ω scans	θmax = 30.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.406, Tmax = 0.870	k = −22→22
37791 measured reflections	l = −29→28

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0237P)2 + 1.8103P] where P = (Fo2 + 2Fc2)/3
6392 reflections	(Δ/σ)max = 0.002
290 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.86 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Br1	1.24046 (3)	0.503519 (12)	0.413433 (9)	0.02077 (6)
S1	0.06464 (7)	0.92776 (3)	0.44296 (2)	0.01447 (9)
Cl1	−0.43250 (7)	0.82410 (3)	0.14834 (2)	0.01568 (9)
S2	0.19587 (8)	0.69303 (3)	0.22076 (2)	0.01861 (10)
O1	0.85351 (19)	0.78959 (8)	0.55746 (6)	0.0141 (3)
O2	0.6219 (2)	0.88767 (8)	0.57238 (6)	0.0178 (3)
O3	0.0131 (2)	0.67996 (9)	0.26280 (7)	0.0221 (3)
N1	0.2804 (2)	0.79823 (9)	0.40883 (7)	0.0124 (3)
N2	−0.0151 (2)	0.81708 (10)	0.34770 (8)	0.0151 (3)
N3	−0.1775 (2)	0.86848 (9)	0.33469 (7)	0.0140 (3)
C1	0.6516 (3)	0.73061 (11)	0.44975 (8)	0.0134 (3)
H1A	0.5825	0.7093	0.4142	0.016*
C2	0.8397 (3)	0.69208 (11)	0.46917 (8)	0.0131 (3)
C3	0.9315 (3)	0.62551 (11)	0.43607 (9)	0.0151 (4)
H3A	0.8693	0.6027	0.3998	0.018*
C4	1.1151 (3)	0.59407 (11)	0.45784 (9)	0.0154 (4)
C5	1.2114 (3)	0.62663 (12)	0.51219 (9)	0.0160 (4)
H5A	1.3353	0.6045	0.5260	0.019*
C6	1.1216 (3)	0.69197 (11)	0.54534 (9)	0.0155 (4)
H6A	1.1836	0.7141	0.5818	0.019*
C7	0.9373 (3)	0.72427 (11)	0.52342 (8)	0.0130 (3)
C8	0.6760 (3)	0.82992 (11)	0.53893 (8)	0.0126 (3)
C9	0.5713 (3)	0.79729 (11)	0.48163 (8)	0.0127 (3)
C10	0.3801 (3)	0.83652 (11)	0.46033 (8)	0.0123 (3)
C11	0.2874 (3)	0.90653 (11)	0.48441 (9)	0.0146 (3)
C12	0.1142 (3)	0.83956 (11)	0.39565 (8)	0.0129 (3)
C13	−0.2802 (3)	0.84836 (11)	0.28434 (8)	0.0135 (3)
H13A	−0.2395	0.8028	0.2594	0.016*
C14	−0.4611 (3)	0.89708 (10)	0.26614 (8)	0.0119 (3)
C15	−0.5571 (3)	0.95147 (11)	0.30911 (8)	0.0140 (3)
H15A	−0.5063	0.9561	0.3506	0.017*
C16	−0.7256 (3)	0.99838 (11)	0.29128 (9)	0.0165 (4)
H16A	−0.7852	1.0351	0.3204	0.020*
C17	−0.8065 (3)	0.99079 (11)	0.22969 (9)	0.0174 (4)
H17A	−0.9203	1.0222	0.2177	0.021*
C18	−0.7171 (3)	0.93639 (11)	0.18634 (9)	0.0159 (4)
H18A	−0.7713	0.9305	0.1454	0.019*
C19	−0.5458 (3)	0.89069 (10)	0.20465 (8)	0.0124 (3)
C20	0.1935 (3)	0.60863 (12)	0.16416 (9)	0.0197 (4)
H20A	0.0794	0.6153	0.1356	0.030*
H20B	0.1828	0.5555	0.1862	0.030*
H20C	0.3170	0.6097	0.1402	0.030*
C21	0.4090 (3)	0.66012 (13)	0.26810 (10)	0.0248 (4)
H21A	0.4260	0.6980	0.3036	0.037*
H21B	0.5291	0.6610	0.2426	0.037*
H21C	0.3864	0.6037	0.2836	0.037*
H11	0.337 (4)	0.9398 (15)	0.5171 (11)	0.028 (6)*
H1N1	0.009 (4)	0.7740 (15)	0.3243 (11)	0.025 (6)*

	U11	U22	U33	U12	U13	U23
Br1	0.01991 (10)	0.02102 (9)	0.02135 (10)	0.00864 (8)	−0.00087 (7)	−0.00287 (8)
S1	0.0134 (2)	0.01564 (19)	0.0143 (2)	0.00403 (17)	−0.00280 (17)	−0.00214 (16)
Cl1	0.0156 (2)	0.01753 (19)	0.01388 (19)	0.00135 (17)	−0.00127 (16)	−0.00306 (15)
S2	0.0189 (2)	0.01360 (19)	0.0234 (2)	−0.00134 (18)	0.00188 (19)	0.00019 (17)
O1	0.0126 (6)	0.0165 (6)	0.0132 (6)	0.0020 (5)	−0.0029 (5)	−0.0014 (5)
O2	0.0173 (7)	0.0198 (6)	0.0162 (6)	0.0021 (5)	−0.0036 (5)	−0.0055 (5)
O3	0.0189 (7)	0.0204 (7)	0.0271 (8)	−0.0024 (6)	0.0065 (6)	−0.0067 (6)
N1	0.0112 (7)	0.0138 (7)	0.0121 (7)	0.0003 (6)	−0.0023 (6)	−0.0013 (5)
N2	0.0135 (7)	0.0161 (7)	0.0157 (7)	0.0036 (6)	−0.0049 (6)	−0.0032 (6)
N3	0.0109 (7)	0.0161 (7)	0.0149 (7)	0.0021 (6)	−0.0014 (6)	0.0019 (6)
C1	0.0133 (8)	0.0157 (8)	0.0111 (8)	−0.0001 (7)	−0.0035 (7)	−0.0002 (6)
C2	0.0110 (8)	0.0149 (8)	0.0134 (8)	−0.0003 (7)	−0.0014 (7)	0.0007 (6)
C3	0.0139 (9)	0.0170 (8)	0.0145 (8)	0.0017 (7)	−0.0028 (7)	−0.0008 (7)
C4	0.0153 (9)	0.0145 (8)	0.0164 (9)	0.0031 (7)	0.0011 (7)	−0.0002 (7)
C5	0.0125 (8)	0.0189 (8)	0.0166 (9)	0.0025 (7)	−0.0028 (7)	0.0038 (7)
C6	0.0146 (9)	0.0183 (8)	0.0136 (8)	−0.0008 (7)	−0.0031 (7)	0.0017 (7)
C7	0.0126 (8)	0.0135 (8)	0.0128 (8)	0.0000 (7)	−0.0004 (7)	−0.0004 (6)
C8	0.0104 (8)	0.0151 (8)	0.0123 (8)	−0.0010 (7)	−0.0004 (6)	0.0014 (6)
C9	0.0110 (8)	0.0150 (8)	0.0120 (8)	−0.0016 (7)	−0.0019 (7)	0.0016 (6)
C10	0.0103 (8)	0.0147 (8)	0.0117 (8)	0.0000 (7)	−0.0017 (6)	0.0010 (6)
C11	0.0128 (8)	0.0162 (8)	0.0147 (8)	0.0009 (7)	−0.0038 (7)	−0.0002 (7)
C12	0.0136 (8)	0.0125 (7)	0.0125 (8)	−0.0001 (7)	0.0002 (7)	0.0005 (6)
C13	0.0123 (8)	0.0135 (8)	0.0146 (8)	0.0010 (7)	−0.0017 (7)	−0.0004 (6)
C14	0.0103 (8)	0.0125 (7)	0.0129 (8)	−0.0014 (6)	−0.0013 (6)	0.0010 (6)
C15	0.0123 (8)	0.0168 (8)	0.0128 (8)	−0.0018 (7)	−0.0015 (7)	0.0013 (7)
C16	0.0159 (9)	0.0165 (8)	0.0172 (8)	0.0010 (7)	−0.0001 (7)	−0.0018 (7)
C17	0.0151 (9)	0.0181 (8)	0.0189 (9)	0.0032 (7)	−0.0022 (7)	0.0015 (7)
C18	0.0154 (9)	0.0178 (8)	0.0144 (8)	0.0004 (7)	−0.0043 (7)	0.0006 (7)
C19	0.0123 (8)	0.0115 (7)	0.0134 (8)	−0.0011 (6)	−0.0002 (7)	−0.0009 (6)
C20	0.0185 (9)	0.0228 (9)	0.0179 (9)	0.0006 (8)	0.0018 (8)	−0.0019 (7)
C21	0.0217 (10)	0.0269 (10)	0.0257 (10)	−0.0002 (9)	−0.0036 (8)	−0.0055 (8)

Br1—C4	1.8986 (18)	C5—H5A	0.9300
S1—C11	1.7273 (18)	C6—C7	1.389 (2)
S1—C12	1.7413 (18)	C6—H6A	0.9300
Cl1—C19	1.7524 (18)	C8—C9	1.469 (2)
S2—O3	1.5130 (15)	C9—C10	1.467 (2)
S2—C20	1.7826 (19)	C10—C11	1.362 (2)
S2—C21	1.785 (2)	C11—H11	0.92 (2)
O1—C7	1.372 (2)	C13—C14	1.464 (2)
O1—C8	1.382 (2)	C13—H13A	0.9300
O2—C8	1.206 (2)	C14—C15	1.399 (2)
N1—C12	1.300 (2)	C14—C19	1.400 (2)
N1—C10	1.393 (2)	C15—C16	1.381 (2)
N2—C12	1.356 (2)	C15—H15A	0.9300
N2—N3	1.366 (2)	C16—C17	1.394 (3)
N2—H1N1	0.85 (2)	C16—H16A	0.9300
N3—C13	1.286 (2)	C17—C18	1.385 (3)
C1—C9	1.356 (2)	C17—H17A	0.9300
C1—C2	1.434 (2)	C18—C19	1.388 (2)
C1—H1A	0.9300	C18—H18A	0.9300
C2—C7	1.394 (2)	C20—H20A	0.9600
C2—C3	1.399 (2)	C20—H20B	0.9600
C3—C4	1.379 (2)	C20—H20C	0.9600
C3—H3A	0.9300	C21—H21A	0.9600
C4—C5	1.394 (2)	C21—H21B	0.9600
C5—C6	1.380 (3)	C21—H21C	0.9600
C11—S1—C12	88.12 (9)	C10—C11—S1	110.64 (13)
O3—S2—C20	106.51 (9)	C10—C11—H11	125.6 (15)
O3—S2—C21	105.18 (10)	S1—C11—H11	123.7 (15)
C20—S2—C21	98.77 (9)	N1—C12—N2	123.02 (16)
C7—O1—C8	122.92 (13)	N1—C12—S1	116.29 (13)
C12—N1—C10	109.50 (15)	N2—C12—S1	120.68 (13)
C12—N2—N3	118.35 (15)	N3—C13—C14	120.14 (16)
C12—N2—H1N1	120.9 (16)	N3—C13—H13A	119.9
N3—N2—H1N1	120.6 (16)	C14—C13—H13A	119.9
C13—N3—N2	114.80 (15)	C15—C14—C19	117.24 (16)
C9—C1—C2	121.96 (16)	C15—C14—C13	121.77 (15)
C9—C1—H1A	119.0	C19—C14—C13	120.99 (16)
C2—C1—H1A	119.0	C16—C15—C14	121.46 (16)
C7—C2—C3	118.67 (16)	C16—C15—H15A	119.3
C7—C2—C1	117.67 (16)	C14—C15—H15A	119.3
C3—C2—C1	123.65 (16)	C15—C16—C17	120.03 (17)
C4—C3—C2	119.21 (16)	C15—C16—H16A	120.0
C4—C3—H3A	120.4	C17—C16—H16A	120.0
C2—C3—H3A	120.4	C18—C17—C16	119.91 (17)
C3—C4—C5	121.69 (17)	C18—C17—H17A	120.0
C3—C4—Br1	119.54 (14)	C16—C17—H17A	120.0
C5—C4—Br1	118.76 (14)	C17—C18—C19	119.39 (16)
C6—C5—C4	119.52 (17)	C17—C18—H18A	120.3
C6—C5—H5A	120.2	C19—C18—H18A	120.3
C4—C5—H5A	120.2	C18—C19—C14	121.95 (16)
C5—C6—C7	119.07 (16)	C18—C19—Cl1	118.43 (13)
C5—C6—H6A	120.5	C14—C19—Cl1	119.61 (13)
C7—C6—H6A	120.5	S2—C20—H20A	109.5
O1—C7—C6	117.31 (15)	S2—C20—H20B	109.5
O1—C7—C2	120.85 (15)	H20A—C20—H20B	109.5
C6—C7—C2	121.84 (17)	S2—C20—H20C	109.5
O2—C8—O1	116.07 (15)	H20A—C20—H20C	109.5
O2—C8—C9	126.89 (16)	H20B—C20—H20C	109.5
O1—C8—C9	117.03 (15)	S2—C21—H21A	109.5
C1—C9—C10	121.02 (15)	S2—C21—H21B	109.5
C1—C9—C8	119.48 (16)	H21A—C21—H21B	109.5
C10—C9—C8	119.50 (16)	S2—C21—H21C	109.5
C11—C10—N1	115.44 (15)	H21A—C21—H21C	109.5
C11—C10—C9	128.05 (16)	H21B—C21—H21C	109.5
N1—C10—C9	116.52 (15)
C12—N2—N3—C13	172.62 (17)	C1—C9—C10—C11	−175.39 (19)
C9—C1—C2—C7	1.4 (3)	C8—C9—C10—C11	5.5 (3)
C9—C1—C2—C3	−177.32 (18)	C1—C9—C10—N1	4.1 (3)
C7—C2—C3—C4	−0.2 (3)	C8—C9—C10—N1	−174.95 (16)
C1—C2—C3—C4	178.50 (17)	N1—C10—C11—S1	0.4 (2)
C2—C3—C4—C5	0.3 (3)	C9—C10—C11—S1	179.94 (15)
C2—C3—C4—Br1	179.80 (14)	C12—S1—C11—C10	−0.06 (15)
C3—C4—C5—C6	0.0 (3)	C10—N1—C12—N2	−179.95 (17)
Br1—C4—C5—C6	−179.46 (14)	C10—N1—C12—S1	0.6 (2)
C4—C5—C6—C7	−0.4 (3)	N3—N2—C12—N1	−175.07 (16)
C8—O1—C7—C6	176.78 (16)	N3—N2—C12—S1	4.4 (2)
C8—O1—C7—C2	−3.3 (3)	C11—S1—C12—N1	−0.32 (15)
C5—C6—C7—O1	−179.58 (16)	C11—S1—C12—N2	−179.80 (16)
C5—C6—C7—C2	0.5 (3)	N2—N3—C13—C14	178.34 (15)
C3—C2—C7—O1	179.92 (16)	N3—C13—C14—C15	−16.2 (3)
C1—C2—C7—O1	1.1 (3)	N3—C13—C14—C19	164.06 (17)
C3—C2—C7—C6	−0.2 (3)	C19—C14—C15—C16	−1.4 (3)
C1—C2—C7—C6	−178.99 (17)	C13—C14—C15—C16	178.83 (17)
C7—O1—C8—O2	−178.27 (16)	C14—C15—C16—C17	1.4 (3)
C7—O1—C8—C9	2.8 (2)	C15—C16—C17—C18	−0.3 (3)
C2—C1—C9—C10	179.09 (16)	C16—C17—C18—C19	−0.8 (3)
C2—C1—C9—C8	−1.8 (3)	C17—C18—C19—C14	0.8 (3)
O2—C8—C9—C1	−179.01 (18)	C17—C18—C19—Cl1	−178.63 (14)
O1—C8—C9—C1	−0.3 (2)	C15—C14—C19—C18	0.3 (3)
O2—C8—C9—C10	0.1 (3)	C13—C14—C19—C18	−179.91 (17)
O1—C8—C9—C10	178.85 (15)	C15—C14—C19—Cl1	179.71 (13)
C12—N1—C10—C11	−0.6 (2)	C13—C14—C19—Cl1	−0.5 (2)
C12—N1—C10—C9	179.78 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N1···S2	0.85 (2)	2.81 (2)	3.5932 (17)	153 (2)
N2—H1N1···O3	0.85 (2)	1.97 (2)	2.808 (2)	169 (3)
C11—H11···O2	0.92 (2)	2.34 (3)	2.869 (2)	116.3 (19)
C13—H13A···O3	0.93	2.55	3.318 (2)	140
C17—H17A···O3i	0.93	2.60	3.285 (2)	131
C20—H20C···O2ii	0.96	2.47	3.431 (2)	176

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N1⋯S2	0.85 (2)	2.81 (2)	3.5932 (17)	153 (2)
N2—H1N1⋯O3	0.85 (2)	1.97 (2)	2.808 (2)	169 (3)
C11—H11⋯O2	0.92 (2)	2.34 (3)	2.869 (2)	116.3 (19)
C13—H13A⋯O3	0.93	2.55	3.318 (2)	140
C17—H17A⋯O3i	0.93	2.60	3.285 (2)	131
C20—H20C⋯O2ii	0.96	2.47	3.431 (2)	176

Symmetry codes: (i) ; (ii) .